Foam dyeing methods using modified indigo compounds

Abstract

The present disclosure provides methods of foam and spray dyeing using modified indigo dye compounds.

1 .- 110 . (canceled) 
     
     
         111 . A method of foam or spray dyeing a substrate, comprising contacting the substrate with a foam or a spray that comprises a dye compound comprising an indigo derivative or a salt thereof,
 wherein the compound is of Formula (I):   
       
         
           
           
               
               
           
         
         wherein: 
         R 1  and R 2  are, independently, H, SO 3 R C , SO 2 R C , PO 3 (R C ) 2 , C(O)NR A R B , C(O)-(optionally substituted C 1-6 alkyl), C(O)-(optionally substituted aryl), C(O)-(optionally substituted C 1-9 glycolyl), C(O)-(optionally substituted heteroaryl), C(O)-(optionally substituted heterocyclyl), C(O)-(optionally substituted C 1-6 hydroxyalkyl), C(O)O-(optionally substituted C 1-6 alkyl), C(O)O-(optionally substituted aryl), C(O)O-(optionally substituted C 1-9 glycolyl), C(O)O-(optionally substituted C 1-6 hydroxyalkyl), C(O)O-(optionally substituted heteroaryl), C(O)O-(optionally substituted heterocyclyl); or 
         R 3  and R 4  are, independently, H, halide, optionally substituted C 1-6 alkyl, optionally substituted C 1-6 hydroxyalkyl, optionally substituted C 1-6 alkoxy, optionally substituted aryl, or SO 3 H; 
         R 7  and R 8  are, independently, H, SO 3 R C , SO 2 R C , PO 3 (R C ) 2 , C(O)NR A R B , C(O)-(optionally substituted C 1-6 alkyl), C(O)-(optionally substituted aryl), C(O)-(optionally substituted C 1-9 glycolyl), C(O)-(optionally substituted C 1-6 hydroxyalkyl), C(O)-(optionally substituted heteroaryl), C(O)-(optionally substituted heterocyclyl), C(O)O-(optionally substituted C 1-6 alkyl), C(O)O-(optionally substituted aryl), C(O)O-(optionally substituted C 1-9 glycolyl), C(O)O-(optionally substituted C 1-6 hydroxyalkyl), C(O)O-(optionally substituted heteroaryl), or C(O)O-(optionally substituted heterocyclyl); 
         R A  and R B  are, independently, H or optionally substituted C 1-6 alkyl, or optionally substituted aryl; 
         R C  is H, optionally substituted C 1-6 alkyl, optionally substituted C 3-6 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted heterocyclyl; 
         m and n are, independently, 0 to 4; 
         or a salt thereof,
 wherein the indigo derivative has a water-solubility of greater than 0.2% w/v in the absence of a reducing agent and in the presence of oxygen, and converts to indigo upon removing the modification, wherein the chemical structure of indigo is the following: 
 
       
       
         
           
           
               
               
           
         
       
     
     
         112 . The method of claim  1 , wherein the foam or spray comprises water. 
     
     
         113 . The method of claim  1 , wherein the foam or spray further comprises one or more additional components selected from the group consisting of an acid, cationic agent, caustic agent, chelating agent, color retention agent, coloring agent, dispersant, foaming agent, hydrolyzing agent, mercerization reagent, penetration enhancer, pH buffering agent, salt, solubilizing agent, stabilizing agent, surfactant, thickening agent, tracer, viscosity modifier, or wetting agent. 
     
     
         114 . The method of claim  3 , wherein the method comprises contacting the substrate with a foam, and wherein the foam comprises a foaming agent present in an amount to provide a stable foam that delivers the dye compound to the substrate and breaks down after application to the substrate and is a nonionic, anionic, cationic, zwitterionic, or amphoteric surfactant. 
     
     
         115 . The method of claim  1 , wherein the foam comprises about 60 to about 95 wt. %, based on the weight of the foam, of a gas. 
     
     
         116 . The method of claim  5 , wherein the foam contains at least about 10% of oxygen. 
     
     
         117 . The method of claim  1 , wherein the method comprises contacting the substrate with a spray, and wherein the spray comprises about 60 to about 95 wt. %, based on the weight of the spray, of water. 
     
     
         118 . The method of claim  1 , further comprising hydrolyzing the dye compound, wherein the hydrolyzing is performed using a base, heat, steam, or a combination thereof. 
     
     
         119 . The method of claim  8 , wherein the base is a hydroxide base, an alkaline earth base, or a carbonate. 
     
     
         120 . The method of claim  1 , further comprising pretreating the substrate prior to the contacting step with a cationic agent or a caustic agent. 
     
     
         121 . The method of claim  1 , wherein the spray or foam lacks a reducing agent to convert the compound to a leuco form of the compound and/or wherein the spray or foam lacks an alkali agent. 
     
     
         122 . The method of claim  1 , wherein the dye compound is not:
 (i) N,N′-dinicotinoyl-[2,2′-biindolinylidene]-3,3′-dione;   (ii) the N″,N′″-methylpyridinium bis(methylsulfate) salt of N,N′-dinicotinoyl-[2,2′-biindolinylidene]-3,3′-dione;   (iii) N,N′-diacetyl-[2,2′-biindolinylidene]-3,3′-dione;   (iv) N,N′-dipropionyl-[2,2′-bi-indolinylidene]-3,3′-dione;   (v) N,N′-di-isobutyryl-[2,2′-biindolinylidene]-3,3′-dione;   (vi) N,N′-dipivaloyl-[2,2′-biindolinylidene]-3,3′-dione;   (vii) N,N′-bis(cyclohexylcarbonyl)-2,2′-bi-indolinylidene-3,3′-dione;   (viii) N,N′-bis(3-phenylpropionyl)-2,2′-bi-indolinylidene-3,3′-dione;   (ix) N,N′-bis(ethoxycarbonylacetyl)-2,2′-bi-indolinylidene-3,3′-dione;   (x) N,N′-bis(2-phenylacetyl)-[2,2′-bi-indolinylidene]-3,3′-dione;   (xi) N,N′-bis-(p-methoxyphenylacetyl) 2,2 ′-bi-indolinylidene-3,3′-dione;   (xii) N,N′-bis(1-naphthylacetyl)-2,2′-bi-indolinylidene-3,3′-dione;   (xiii) N,N′-bis(2-phenylbutyryl)-2,2′-indolinylidene-3,3′-dione;   (xiv) (E)-1,1′-di(adamantane-1-carbonyl)-[2,2′-biindolinylidene]-3,3′-dione.   (xv) 1H,1′H-[2,2′-biindole]-3,3′-diyl diacetate;   (xvi) 3,3′-bis(phenylacetoxy)-2,2′-bi-indolyl;   (xvii) 3,3′-bis(p-methoxyphenylacetoxy)-2,2′-bi-indolyl;   (xviii) 3,3′-bis(1-napthylacetoxy)-2,2′-bi-indolyl;   (xix) 3,3′-bis(phenylbutyryloxy)-2,2′-bi-indolyl;   (xx) 3,3′-bis(pivaloyloxy)-2,2′-bi-indolyl;   (xxi) 3,3′-bis(1-adamantylcarbonyloxy)-2,2′-bi-indolyl; or   (xxii) 3,3′-bis(ethoxycarbonylacetoxy)-2,2′-bi-indolyl.   
     
     
         123 . The method of claim  1 , wherein, R 3  and R 4  are not H, when R 1  and R 2  are both 1-methyl-pyridyl-3-yl. 
     
     
         124 . The method of claim  1 , wherein one or both of R 1  or R 2  is H. 
     
     
         125 . The method of claim  1 , wherein one or both of R 1  and R 2  is C(O)-(optionally substituted pyridyl). 
     
     
         126 . The method of claim  15 , wherein the optionally substituted pyridyl is substituted on the N atom with C 1-6 alkyl. 
     
     
         127 . The method of claim  1 , wherein the compound is an acid or base addition salt. 
     
     
         128 . The method of claim  1 , wherein the compound is of Formula (IB) or (IC): 
       
         
           
           
               
               
           
         
         wherein:
 R 5  and R 6  are, independently, H or C 1-6 alkyl; and 
 X is halide, sulfate, C 1-6 alkylsulfate, bisulfate, or phosphate. 
 
       
     
     
         129 . The method of claim  1 , wherein the compound is: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein X is a counteranion. 
       
     
     
         130 . The method of claim  1 , wherein the compound is: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       or a salt thereof.